Gem-bis amide herbicide antidote compositions and methods of use

ABSTRACT

Herbicidal compositions comprising an active herbicidal compound and antidote therefor and methods of use; the antidote compound corresponds to substituted gem-bis amides having the formula in which R is selected from the group alkyl, alkenyl, phenyl, phenalkenyl, naphthyl, cyanoalkyl, and substituted phenyl wherein said substituents are selected from the group methoxy, nitro, chloro, bromo,3,4-methylenedioxy, mono- and di-substituted lower alkyl; and R1 is lower haloalkyl.

Hittite Stats Teach [451 Dec.2, 1975 1 GEM-BIS AMIDE HERBICIDE ANTIDOTE COMPOSITIONS AND METHODS OF USE [75] Inventor: Eugene G. Teach, El Cerrito, Calif.

[73] Assignee: Stauffer Chemical Company,

Westport, Conn.

[22] Filed: May 24, 1973 [21] Appl. No: 363,464

OTHER PUBLICATIONS Bingham et a1., Prelim. Eval. of Several Materials etc, (1959), CA 54, p7 25492, (1960). Meade et 211., Pre-and Post Emergence Weed Control, etc," (1959), CA 54, p. 21605, (1960).

Primary Examiner-Glennon H. H011I'2lh Attorney. Agent, or Firm-Harry A. Pacini [57] ABSTRACT Herbicidal compositions comprising an active herbicidal compound and antidote therefor and methods of use; the antidote compound corresponds to substituted gem-bis amides having the formula in which R is selected from the group alkyl, alkenyl. phenyl, phenalkenyl. naphthyl. cyanoalkyl. and substituted phenyl wherein said substituents are selected from the group methoxy, nitro, chloro, bromo.3 4- methylenedioxy, monoand di-substituted lower ulkyl; and R is lower haloalkyl.

7 Claims, N0 Drawings GEM-BIS AMIDE HERBICIDE ANTIDOTE COMPOSITIONS AND METHODS OF USE BACKGROUND OF THE INVENTION Among the many herbicidal compounds commercially available, the thiocarbamates alone or admixed with other herbicides, such as the triazines, have reached a relatively high degree of commercial success. These herbicides are immediately toxic to a large number of weed pests at different concentrations varying with the resistance of the weed pests. Some examples of these compounds are described and claimed in the US. Pat. Nos. 2,913,327, 3,037,853, 3,175,897, 3,185,720, 3,198,786 and 3,582,314. It has been found in practice that the use of these thiocarbamates as herbicides on crops sometimes causes serious injuries to the crop plant. When used in the recommended amounts in the soil to control many broadleaf weeds and grasses, seri ous malformation and stunting of the crop plants result. This abnormal growth in the crop plants results in loss of crop yield. Previous attempts to overcome this problem involves the treatment of the crop seed with certain antagonistic agents prior to plants, see US. Pat. Nos. 3,131,509 and 3,564,768. These antagonistic agents have not been notably successful. The aforementioned patent specifically exemplifies the treatment of seeds employing compounds ofa different chemical class not suggestive of the present invention.

DESCRIPTION OF THE INVENTION It has been discovered that plants can be protected against injury by the thiocarbamate-type herbicides, alone or mixed with other compounds and/or the tolerance of the plants can be substantiallyincreased to the active compounds of the above-noted U.S'.Patents by adding to the soil an antidote compound corresponding to the following formula:

in which R is selected from the group alkyl, alkenyl, phenyl, phenalkenyl, naphthyl, cyanoalkyl and substituted phenyl wherein said substituents are selected from the group methoxy, nitro, chloro, bromo, 3,4- methylenedioxy, monoand di-substituted lower alkyl; and R, is lower haloalkyl.

In theabove description, the following embodiments are intended for the various substituent groups: For R lower haloalkyl preferably includes, unless otherwise provided, those members which contain from 1 to 4 carbon atoms, inclusive, in both straight chain and branched chain configurations and the term halo includes chloro and bromo as mono-, di-, tri-. tetraand persubstitutions, more preferably, monochloromethyl and dichloromcthyl. For R. alkyl preferably includes those members containing from 1 to 6 carbon atoms, inclusive, ,in ,both branched andstraight chain configuration; alkenyl preferably includes those members containing at least one olefinic double bond and from 2 to 6 carbon. atomsfinclusive. in both 10 R,.phenyl substituted wherein the substituents are monoand disubstituted lower alkyl is meant tolyl and xylyl, i.e., monomethylphenyl and dimethylphenyl substitution and also includes other lower alkyl moieties having from 1 to 4 carbon atoms, inclusive, in branched chain and straight chain configurations.

As an alternative mode of action. the compounds of this invention may interfere with the normal herbicidal action of the thiocarbamate-type and other herbicides to render them selective in their action. Whichever mode of action is present, the corresponding beneficial and desirable effect is the continued herbicidal effect of the thiocarbamate with the accompanying decreased herbicidal effect on desired crop species. This advantage and utility will become more apparent hereinafter.

Therefore, the terms herbicide, antidote or antidotal amount, is meant to describe that effect which tends to counteract the normal injurious herbicidal response that the herbicide might otherwise produce. Whether it is to be termed a remedy, interferant, protectant, or the like, will depend upon the exact mode of action. The mode of action is varied, but the effect, which is desirable, is the result of the method of treating the soil in which a crop is planted. Hitherto. there have been no systems which have been satisfactory for this purpose.

The compounds of this invention represented by the above formula can be prepared by several different procedures depending upon the starting materials.

The gem-bis-amides of this invention can be prepared by combining an aldehyde with an amide and an acid catalyst. such as p-toluene sulfonic acid. in a 501- vent. such as benzene or toluene. The reaction mixture is heated at reflux until the theoretical amount of water is removed with a Dean-Stark apparatus. Most of the products were solids which crystallized out of the solvent on cooling, therefore. after the reaction is complete, the end product is readily recovered by normal work-up procedures.

The compounds of the present invention and their preparation are more particularly illustrated by the following examples. Following the examples of preparation is a table of compounds which are prepared according to the procedures described herein. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

EXAMPLE 1 Preparation of a, a-bis-dichlo roacetamido-4-nitro toluene.

Dichloroacetamide. 6.4 g., p-rnitrobenzaldehyde, 3.8 g., and p-toluene sulfonic acid. 0.1 g. are combined in ml. of'toluene and heated at reflux until 0.5 ml. of wateris removed in a Dean-Stark apparatus. The product, which crystallizes from the toluene solution, weighs 7.6 g. and melts at 224-227C. with decomposition.,

EXAMPLE 11 Preparation of 1.1 -bis-dichloroacetamido-3-phenyl-3-propene.

Cinnamaldehyde. 2.6 g.. dichloroacctamide. 5.1 g.. and p-toluene sulfonic acid. 0.1 g.. are heated to reflux in 100 ml. of toluene under a Dean-Stark apparatus until 0.4 ml. of water is removed. The product is recovered by filtration. A sample of the title compound triturated with ether had a melting point of 168-170C. with decomposition.

EXAMPLE III Preparation of a, a-bis-dichloroacetamido butane.

Butyraldehyde. 2.2 g., dichloroacetamide. 7.7 g.. and p-toluene sulfonic acid. 0.5 g. are combined in 100 ml. of benzene and heated to reflux under a Dean-Stark apparatus. After 1 hour. 0.5 ml. of water is removed and the mixture is cooled and the product recovered by filtration. The yield of title compound is 2.6 g.. m.p. 165168C. Additional product is recovered by removing the benzene under vacuum.

EXAMPLE 1V Preparation of a. a-bis-chloroacetamido toluene.

Benzaldehyde. 4.2 g.. is combined with 7.5 g. of chloroacetamide and 0.5 g. of p-toluene sulfonic acid in 100 ml. of toluene. The mixture is heated at reflux under a Dean-Stark apparatus until 0.75 ml. of water has been removed. The product which crystallized out on cooling weighed 10.1 g. and melted at 192-l95C.

EXAMPLE V Preparation of 1.1-bis-dichloroacetamido-2,2-dimethyl-4-cyano butane.

lbanitrile. 3.1 g.. dichloroacetamide. 6.4 g.. and 0.1 g. p-toluene sulfonic acid are combined in 100 ml. of toluene and heated at reflux under a Dean-Stark apparatus until 0.5 ml. of water is recovered. The product which is soluble in toluene was obtained by removing the toluene under vacuum. There is obtained 4.4 g. of

TABLE l-continued (i /NHlR RC1-\ NHCR O COMPOUND m.p. C. NUMBER R R or N 17 l-naphthyl CHCI 211-213 18 p-i-C;,H -phenyl CHCL; 210-211 19 2.5-CH;,O-phen vl CHCL; 201-202 20 3.4-CH;,O-phenyl CHCL; 192-195 21 n-C;,H CHCL; -168 21 n-C;,H CH CI 162-163 23 i-C;,H CH C1 -186 24 C H; CHC1 Z 14 25 n1-NO -phenyl CHCL; 149 26 CH =CH CHCI 142-150 27 H CH CI 192-195 28 m-No -phcnyl CH CI 197-199 29 2.6-Cl-phenyl CHCL; 199-201 3O CHCl 1.4650

The compounds of this invention were employed in effective herbicidal antidote compositions comprising thiocarbamates in combination with antidote compounds described hereinabove. They were tested in the following manner.

PROCEDURE: MULTlCROP ANTIDOTE SCREEN Plastic flats were filled with Felton loamy sand soil. Since a variety of grass and broadleaf crops were used in these tests. EPTAM (EPTC) was incorporated at A and 5 lb/A., while a constant rate of 5 lb/A. of the additive was used. LASSO (2-chloro-2',6-diethy1-N-(methoxymethyl)acetanilide, EPTAM (EPTC) and the herbicide antidote were applied separately by pipetting measured amounts of the appropriate stock solutions into the soil during incorporation in a 5 gallon rotary cement mixer. Stock solutions were prepared as follows:

A. #2 lb/A.: 670 mg. of EPTC 6E (75.5% a.i.) is diluted with 500 ml. of deionized water so that 2 ml. equals vs lb/A. flat.

B. 5 1b/A.: 6700 mg. of EPTC 6E (75.5%) is diluted with 500 ml. of deionized water so that 2 ml. equals 5 lb/A. flat.

C. 2 lb/A.: 427 mg. LASSO 4E is diluted with 100 ml. of deionized water so that 1 ml. equals 2.05 mg. (a.i.) and 4 m1. equals 8.2 mg. equivalent to 21b/A. flat.

Antidote stock solutions are prepared by diluting 102 mg. of technical material with 10 ml. of acetone 1% Tween 20 (polyoxyethylene sorbitan monolaurate) so that 2 ml. equals 5 lb/A. flat.

After the soil is treated with both herbicide and additive, the soil is transferred from the mixer back into the flat where it is then prepared for seeding. The initial step in preparation is to remove a one pint sample of soil from each flat to be retained and used to cover the seeds after planting. The soil is then leveled and rows one-quarter inch deep are made in each flat. Flats treated with 5 lb/A. of EPTAM are seeded to DeKalb XL-44 corn (Zea niaize). US H9 sugarbeets (Beta vulgare). small seeded gray striped sunflower (Helianrhus annus), Acala cotton (Gossypium hirsutum), Brag soybeans (Glycine max) and oilseed rape (Brassica napus). Flats treated with /2 lb/A. of EPTAM are seeded to red oats (Avena byzanlinu), R-IO milo (Sorghum vulgare), Fremont HRS wheat (Triticum aestivum), giant foxtail (Seteria feberii), Calrose rice (Oryza saliva) and Blue Mariate barley (Hordeum vulgare). Flats treated with 2 lb/A. of LASSO are seeded to DeKalb XL-44 corn (Zea maize), Fremont HRS wheat (Triticum aesrivum), Calrose rice (Oryza sativa), R-IO milo (Sorghum vulgare), and Numar barley (Hordeum vulgare). Seeds are then covered with the pint soil sample removed prior to seeding.

The flats are then placed on greenhouse benches where temperatures are maintained between 7090F. The soil is watered by sprinkling to assure good plant growth.

Injury ratings are taken 2 to 4 weeks after the treatments are applied. Soil treated with the herbicides alone at /2, 2 or 5 lb/A. is included to provide a basis for determining the amount of injury reduction provided by the herbicide antidotes. The per cent protection is determined by a comparison with flats not treated with the candidate antidote.

TABLE II Multicrop Screen Results Per Cent Protection COMPOUND Rate of Protection NUMBER Herbicide lb/A. Crop (4 weeks) I LASSO** 2.0 wheat 40" LASSO 2.0 milo 37" EPTC* 5.0 com 100 2 EPTC 0.5 wheat 100 LASSO 2.0 milo 37" EPTC 0.5 barley I EPTC 5.0 com 100 3 EPTC 0.5 milo 67 LASSO 2.0 milo 26" 4 LASSO 2.0 wheat l8" 5 EPTC 50 com 90 6 LASSO 2.0 wheat 30" EPTC 0.5 barley 8O EPTC 5.0 corn I00 7 EPTC 5.0 com 70 8 EPTC 5.0 corn I00 9 EPTC 5.0 corn I00 10 EPTC 5.0 com 100 I l LASSO 2.0 milo l5" LASSO 2.0 wheat 40" EPTC 5.0 corn I00 l2 EPTC 5.0 corn I00 l3 LASSO 2.0 wheat 50 LASSO 2.0 milo 47 EPTC 0.5 barley 75 EPTC 5.0 corn I00 l4 EPTC 0.5 milo 40 EPTC 0.5 wheat EPTC 0.5 barley I00 EPTC 5.0 corn I00 I5 EPTC 50 com I00 16 E TC 5.0 com I00 17 E TC 5.0 corn I00 l8 EPTC 5.0 com 100 I9 EPTC 5.0 corn 100 20 EPTC 5.0 corn I00 21 EPTC 0.5 wheat 20 EPTC 5.0 corn I00 22 EPTC 0.5 milo 22 EPTC 5.0 com 23 23 LASSO 2.0 wheat 40" LASSO 2.0 milo 26" EPTC 0.5 milo 22 EPTC 0.5 wheat 20 EPTC 5.0 com 22 30 LASSO 2.0 wheat 30" "S-ethyl dipropylthiocarbamare *2-chloro-2'.6diethyl-N-(methnxymethyl) acetanilide "2 weeks CORN SEED TREATMENT TEST Small flats were filled with Felton loamy sand soil. Soil incorporated herbicides were applied at this time. The soil from each flat was placed into a five-gallon cement mixer where the soil was mixed as the herbicides were applied using a predetermined amount of a stock solution containing 936 mg. of 75.5% active ingredient to 100 ml. of water. One ml. of stock solution was applied to the soil in a volumetric pipet for each pound of herbicide desired. One ml. of stock solution contained 7 mg. of herbicide which equals one pound per acre when applied to the soil in the flats. After the herbicide incorporation the soil was placed back into the flats.

Flats of herbicide-treated and untreated soil were then ready to be planted. A pint sample of soil was removed from each flat and placed next to each flat for later use in covering up the seeds. The soil was leveled and rows one-half inch deep were made for planting seeds. Alternating rows of treated and untreated crop seeds were sown. In each test. six PAG 344T field corn seeds were planted in each row. Rows were approximately l- /2 inches apart in the flat. Seeds were treated by placing 50 mg. of the antidote compound with 10 grams of corn seed (0.5% w/w) in a suitable container and shaking them until the seeds were uniformly covered with the compound. Antidote compounds were also applied as liquid slurries and powders or dusts. In some cases, acetone was used] to dissolve powdered or solid compounds so they could be more effectively applied to the seeds.

After the flats were seeded, they were covered with the one pint of soil which had. been removed just prior to planting. Flats were placed on greenhouse benches where temperatures ranged from 90F. Flats were watered by sprinkling as needed to assure good plant growth. Per cent control ratings were taken two. three and four weeks after the treatments were applied.

In each test, the herbicide was applied alone. in combination with the seed protect-ant, and the seed protectant was applied alone to check for phytotoxicity. The degree of the protective effect was noted by comparison with the control. The results of these tests are tabulated in Table III.

TABLE III Per Cent Injury to Corn from EPTC* (6 lb/A.) Seed Treatment Test Per Cent Protection. 2 weeks Treated COMPOUND Seed NUMBER (0.5% w/w) S-ethyl dipropylthiocarbamate derstood. however, that the herbicides can be incorporated into the soil and thereafter the antidote compound can be incorporated into the soil. Moreover. the crop seed itself can be treated with a non-phytotoxic quantity of the compound and planted into the soil which has been treated with herbicides, or untreated with the herbicide and subsequently treated with the herbicide. The addition of the antidote compound does not affect the herbicidal activity of the herbicides.

The amount of antidote compound present can range between about 0.01 to about parts by weight of antidote compound described herein per each part by weight of herbicide. The exact amount of antidote compound will usually be determined on economic ratios for the most effective amount usable. it is understood that a non-phytotoxic quantity of antidote compound will be employed in the herbicidal compositions described herein.

The herbicides indicated in the tables and elsewhere are used at rates which produce effective control of undesirable vegetation The rates are within the recommended amounts set forth by the supplier. Therefore. the weed control in each instance is commercially acceptable within the desired or recommended amount.

It is clear that the classes of herbicidal agents described and illustrated herein are characterized as effective herbicides exhibiting such activity. The degree of this herbicidal activity varies among specific compounds and among combinations of specific compounds within the classes. Similarly, the degree of activity to some extent varies among the species of plants to which a specific herbicidal compound or combination may be applied. Thus. selection of a specific herbicidal compound or combination to control undesirable plant species readily may be made. Within the present invention are prevention ofinjury to a desired crop spe eies in the presence of a specific compound or combination may be achieved. The beneficial plant species which can be protected by this method is not intended to be limited by the specific crops employed in the examples.

The herbicidal compounds employed in the utility 'of this invention are active herbicides of a generall type. That is, the members of the classes are herbicidally effective against a wide range of plant species with no discrimination between desirable and undesirable species. The method of controlling vegetation comprises apply ing an herbicidally effective amount of the hereindescribed herbicidal compounds to the area or plant locus where control is desired. The compositions as set forth in this invention include those wherein the preferred active herbicidal compound is selected from EPTC. S- ethyl diisobutyl thiocarbamate. S-propyl dipropyl thiocarbamate. 5-2.3.3-trichloroallyl-diisopropyl thiocarbamate. S-ethyl cyclohexyl ethyl thiocarbamate. 2- ehloro-2',6'-diethyl-N-(rnethoxymethyl)acetanilide. S-ethyl hexahydro-lH-azepine-l-carbothioate. 2- chloro-N-isopropylacetanilidc. N.N-diallyl-2- chloroacetamide. S-4-chlorobenzyl diethyl thiocarba mate. 2-chloro-4-ethylamino-6-isopropylaminos-triazine. 2-chloro-4.6-bis(ethylamino)-s-triazine. 2(4- chloro6-ethylamine-s-triazine-Z-yl-amino)-2-methylpropionitrile. 2-chloro-4-cyelopropylamino-(i-isopropylamino-s-triazine, 2.4-dichlorophenoxyaeetic acid, its esters and salts. and 3-)3.4-dichlorophenoxyacetic acid. its esters and salts. and 3-( 3.4-dichlorophenyl)-l,l-dimethylurea and combination thereof.

An herbicide as used herein means a compound which controls or modifies the growth of vegetation or plants. Such controlling or modifying effects include all deviations from natural development; for example. killing. retardation. defoliation. desiccation. regulation. stunting. tillering. stimulation. dwarfing and the like. By plants/I it is meant germinant seeds. emerging seedlings. and established vegetation. including the roots and above-ground portions What is claimed is:

1. An herbicide composition comprising a mixture of a herbicidally effective amount ofa thiocarbamate herbicide and an antidote compound corresponding to the formula in which R is substituted phenyl wherein said substituent is 3,4-methylenedioxy; and R, is lower chloroalkyl containing from 1 to 4 carbon atoms, inclusive; from about 0.01 to about 15 parts by weight of antidote compound for each part by weight of the thiocarbamate herbicide.

2. The composition according to claim 1 in which R is diehloromethyl.

3. in the method of controlling weeds wherein a thiocarbamate herbicide is applied to the habitat of said weeds. the improvement comprising applying to the habitat thereof from which about 0.01 to about 15 parts by weight for each part by weight of the thiocarbamate herbicide an antidote compound corresponding to the formula in which R is substituted phenyl wherein said substituent is 3.4-methylenedioxy'. and R is lower chloroalkyl containing from 1 to 4 carbon atoms. inclusive.

4. The method of protecting corn crop from injury due to a thiocarbamate herbicide. comprising applying to the corn seed prior to planting a non-phytotoxic antidotally effective amount of a compound corresponding to the formula in which R is substituted phenyl wherein said substituent is 3.4-methylenedioxy; and R is lower chloroalkyl containing from i to 4 carbon atoms. inclusive.

It] in which R is substituted phenyl wherein said substituent is 3,4-methylenedioxy; and R is lower chloroalkyl containing from 1 to 4 carbon atoms, inclusive.

6. The method according to claim 4 in which said thiocarbamate herbicide is S-ethyl dipropylthiocarbamate, and in which R is 3,4-methylenedioxyphenyl and R is dichloromethyl.

7. The method according to claim 5 in which said thiocarbamate herbicide is S-ethyl dipropylthiocarbamate, and in which R is 3,4-methylenedioxyphenyl and R is dichloromethyl. 

1. AN HERBICIDE COMPOSITION COMPRISING A MIXTURE OF A HERBICIDALLY EFFECTIVE AMOUNT OF A THIOCARBAMATE HERBICIDE AND AN ANTIDOTE COMPOUND CORRESPONDING TO THE FORMULA
 2. The composition according to claim 1 in which R1 is dichloromethyl.
 3. In the method of controlling weeds wherein a thiocarbamate herbicide is applied to the habitat of said weeds, the improvement comprising applying to the habitat thereof from which about 0.01 to about 15 parts by weight for each part by weight of the thiocarbamate herbicide an antidote compound corresponding to the formula
 4. The method of protecting corn crop from injury due to a thiocarbamate herbicide, comprising applying to the corn seed prior to planting a non-phytotoxic antidotally effective amount of a compound corresponding to the formula
 5. The method of protecting corn crop from injury due to a thiocarbamate herbicide, comprising pre-plant incorporation in the soil in which said corn crop is to be planted, from about 0.01 to about 15 parts by weight for each part by weight of the thiocarbamate herbicide, a non-phytotoxic antidotally effective amount of a compound corresponding to the formula
 6. The method according to claim 4 in which said thiocarbamate herbicide is S-ethyl dipropylthiocarbamate, and in which R is 3, 4-methylenedioxyphenyl and R1 is dichloromethyl.
 7. The method according to claim 5 in which said thiocarbamate herbicide is S-ethyl dipropylthiocarbamate, and in which R is 3, 4-methylenedioxyphenyl and R1 is dichloromethyl. 